A system for determination of manganese, after preconcentration with 3% (w/w) 1-(2-pyridylazo)-2-naphthol (PAN), adsorbed on microcrystalline naphthalene is proposed. An amount of 200mg of this complexing mixture is placed in a glass column and conditioned with a NH(4)Cl/NH(4)OH buffer solution (pH 9.5). The aqueous sample, containing manganese, is treated with an ammonium tartrate solution, then with a hydroxylammonium chloride solution and, finally, with a buffer solution. The resulting solution is passed through the column containing microcrystalline naphthalene modified with 1-(2-pyridylazo)-2-naphthol (PAN) where Mn(II) is retained. The column is first washed with deionized water and then with 10.0ml of dimethylformamide to dissolve the Mn(II)-PAN/naphthalene complex. Manganese is determined by air-acetylene flame atomic absorption spectrometry. About 1mug of manganese can be concentrated from 200ml of aqueous sample, allowing a preconcentration factor of 20, a limit of quantification of 5ngml(-1) and R.S.D. of 3.8%. The accuracy was ascertained using certified reference materials, including samples of urine and glass. Water samples were also analysed and the results are in good agreement with those obtained by graphite furnace atomic absorption spectrometry.